CN115513471A - Screen printing preparation method of self-supporting oxygen evolution anode - Google Patents
Screen printing preparation method of self-supporting oxygen evolution anode Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 146
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000001301 oxygen Substances 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 238000007650 screen-printing Methods 0.000 title claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 33
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- 229910002640 NiOOH Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
- H01M4/8835—Screen printing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a screen printing preparation method of a self-supporting oxygen evolution anode, which has the advantages that: (1) The preparation process of the screen printing is adopted, the process is simple, the quality control is easy to realize, the process repeatability is good, and the method is suitable for batch preparation of large-area OER electrodes; the prepared oxygen evolution anode has higher repeatability and uniformity and is far superior to commercial IrO 2 、RuO 2 The performance of the electrode. (2) In the screen printing process, a three-dimensional NiFeM-LDH self-supporting structure is formed by in-situ growth, so that the stability and the conductivity of the electrode are enhanced, and the release of an oxygen product is facilitated; the polymer adhesive which is not beneficial to conductivity is not needed, so that the conductivity is further enhanced; no noble metal load. (3) The oxygen evolution catalytic performance is greatly improved through an etching process, a third component doping and a heat treatment process, and the obtained oxygen evolution anode has extremely high oxygen evolution activity, stability and repeatability.
Description
Technical Field
The invention belongs to the field of water electrolysis, and particularly relates to a screen printing preparation method of a self-supporting oxygen evolution anode.
Background
Currently, as environmental problems due to the over-utilization of fossil fuels become more serious, the development of new environmentally friendly energy carriers as substitutes for conventional fossil fuels has become an urgent need of the whole society. Hydrogen has become one of the most potential alternative fuels in the future due to its advantages of high mass-to-energy density, clean and efficient energy conversion, etc.
The industrial mature large-scale hydrogen production process mainly comprises methane reforming and coal gasification hydrogen production technologies, but the two technologies have the defects of large energy loss, trace CO, high carbon dioxide emission and the like, and are difficult to be suitable for the application requirement of the current main carrier for hydrogen energy utilization, namely a fuel cell. However, hydrogen production by alkaline water electrolysis has attracted attention as a main method for green hydrogen production in recent years due to its advantages of high technical maturity, simple process, high purity of produced hydrogen, and the like.
In a reactor/electrolytic cell for producing hydrogen by the electrolysis of alkaline water, an electrode material is a site of electrochemical reaction and is a core component of the reactor. Wherein, the oxygen evolution reaction on the surface of the anode relates to a 4 electron transfer process, and the slow electrode process dynamics limits the improvement of the hydrogen production efficiency by the alkaline water electrolysis. Therefore, designing and developing a batch preparation process of the non-noble metal oxygen evolution anode with high performance and easy amplification is always a research hotspot in the field of water electrolysis.
Conventional noble metal electrode materials such as iridium, ruthenium, platinum and the like have been used for oxygen evolution electrode materials at the earliest time, and are widely used for anodes for pure water electrolysis and alkaline water electrolysis. However, in industrial applications for large-scale green hydrogen production, the high cost of materials has significantly increased the difficulty of large-scale conversion thereof. (Q.Gao et al.structural and electronic modulation of transition-metal-bipolar catalysts solutions [ J ]. Advanced materials,2019,31 (2)), finding non-noble metal oxygen evolution materials to replace noble metals has significant application value.
In the development of non-noble metal OER materials, transition group metals such as iron, cobalt, nickel, molybdenum and the like exhibit high oxygen evolution activity due to the incompletely filled d-orbitals. Among them, niFe layered double hydroxide (NiFe-LDH) has become one of the most promising oxygen evolution materials. (J.Wang et al.Recentprogress in cobalt-based heterogeneous catalysts forelectrochemical water splitting[J]Advanced Materials,2016,28 (2): 215-230.) Corrigan et al (D.A. Corrigan. The Catalysis of the Oxygen Evolution Reaction by Iron oxides in Thin Film Oxide Electrodes [ J.]J.Electrochem.Soc,1987,134, 377-384.) for the first time, reported the catalytic synergy of Fe with Ni-based electrocatalytic materials in alkaline medium oxygen evolution reactions, they incorporated Fe into NiO x Or Ni (OH) 2 The overpotential of the interface under the condition of 25% iron doping is only 320mV, which is far lower than 380mV of the material without doped iron element. M.S.Burke et al (M.S.Burke et al. Cobalt-Iron (Oxy) hydroxide Oxygen Evolution electrolytes: the Role of Structure and Composition on Activity, stabilty, and Mechanism [ J. ]]J.am.chem.soc,2015,137 2 Film interface OER performance. The research result shows that: after one week of storage in KOH rich in Fe, ni (OH) 2 The initial overpotential of the film was reduced by about 50mV; meanwhile, the characteristic peak of the oxidation conversion from nickel hydroxide to hydroxyl group shifts from 0.43V to 0.51V, which indicates that Fe, ni (OH) is doped in the electrolyte 2 Conversion of catalytic interface structures from NiOOH to Ni 1-x Fe x (OOH), the high activity of the iron-based active sites in the mixed cation phase, is a major cause of the improvement in OER performance at the catalytic interface.
Although LDH-based materials have the advantages of low cost, ease of preparation, good durability and low electrical conductivity, in practical applications, they generally need to be mixed with a binder to prepare an electrode. The introduction of a non-conductive adhesive tends to have two adverse effects on OER: firstly, the charge transfer resistance of an electrode/solution interface is increased; secondly, the bubbles formed by OER can break the connection between the powdered LDH and the binder, resulting in the catalytic layer collapsing. (J.Hou et al. Rationaldesign of nanoarray architecture for electrochemical water separation [ J ]. Advanced Functional Materials,2019,29 (20).) for this reason, the preparation process does not require the presence of a binder, and NiFe-LDH electrodes with a self-supporting structure are of great interest in the development.
Current methods for preparing self-supporting NiFe-LDH electrodes generally have ionsExchange method, hydrothermal method, electrodeposition method. Luo Yu et al (L.Yu et al. Cu nanowire shells with NiFe-layered double hydroxide as a binary electro-catalyst for over water splitting [ J.].Energy&Enviromentalcience, 2017,10 (8): 1820-1827.) 2D NiFe-LDH nanowires are electrodeposited on self-made copper nanowires, and self-supporting three-dimensional core-shell structure Cu @ NiFe-LDH electrodes are prepared. It is at 10mA cm -2 The overpotential is as low as 199mV,1A cm -2 The overpotential is only 315mV. Qiu Yang et al (Q. Yang et al. High structural constraint of an ultra in a layered double hydroxide nanoarray for high-efficiency oxygen evolution reaction [ J. Yang et al]Nanoscale,2014,6 (20): 11789-11794.) A layered NiCoFe-LDH structure was prepared by a two-step hydrothermal method at 30 mA-cm -2 The overpotential of 233mV is provided, and compared with 438mV of a material prepared by non-self-supporting, the overpotential is obviously improved. Bin Liu et al (Bin Liu, et al. Amorphous Multimetal Alloy Oxygen evolution Catalysts [ J)]ACS Materials Letters,2020,2 (6): 624-632.) NiFeMoB alloys were prepared by a room temperature synthesis at 500mA cm -2 The lowest OER overpotential is only 220mV. Zhang Xin He et al (ZL 2020106255211) patent discloses a method for preparing a NiFe-LDH three-dimensional self-supporting OER electrode containing high valence iron. They prepare NiFe-LDH electrode containing high valence state iron in situ on foam nickel skeleton through hydrothermal reaction at 1 mol.L -1 KOH electrolyte solution of (2) as oxygen evolution anode with current density of 10 mA-cm -2 When the current density is 500mA cm, the oxygen evolution overpotential is 239mV -2 The oxygen evolution overpotential is 350mV. Gunn-Dongsheng et al (ZL 2020112489048) disclose a hydrothermal synthesis process for preparing NiFe-LDH. The preparation process comprises the following steps: firstly, cu is loaded on a foam nickel framework through a hydrothermal method, and then a self-supporting NiFe-LDH nano array structure is grown on the surface of the foam nickel framework in situ through the hydrothermal method. The oxygen evolution anode is 1 mol.L -1 In a KOH electrolyte solution of (2), at 10mA · cm -2 The OER overpotential is 226mV. However, in practical operation, such hydrothermal method is limited by the reaction equipment, and large-scale production cannot be realized. Zhengzongxin et al (ZL 201810337104X) disclose a preparation method suitable for large-area self-supporting oxygen evolution electrode. The specific preparation process flow is as follows: firstly, a layer of alkaline oxide is loaded on a conductive substrate, and then the conductive substrate is soaked into a transition metal mixed salt solution for reaction, aiming at vertically and directionally growing ultrathin transition single metal and multi-metal hydroxides on the conductive substrate to obtain the self-supporting high-performance oxygen evolution electrode. The oxygen evolution anode is at 50mA cm -2 The oxygen evolution overpotential is about 300mV.
In conclusion, although the self-supported LDH material has excellent oxygen evolution activity, there are only few patent reports on a preparation process for batch preparation, which can ensure the repeatability and uniformity of the electrode. In the preparation process of the self-supporting LDH material, the ion exchange method needs to prepare a pure-phase hydroxide layer, and the growth conditions are not easy to control; in the hydrothermal synthesis process, a surfactant is often required to be added in order to obtain a better lamellar structure, the material preparation is limited by reaction equipment, and large-area batch preparation of lamellar electrodes cannot be realized easily; although the electrodeposition method can grow two-dimensional materials on a conductive substrate, the uniform growth of the two-dimensional materials is difficult to realize by the complicated current distribution of an electrochemical system in the process of large-area electrode deposition.
Disclosure of Invention
Aiming at the problems in the OER preparation technology, the invention aims to provide a screen printing preparation method suitable for self-supporting oxygen evolution NiFeM-LDH (M = Mo, mn, co, W, P, B and the like) series anodes. The in-situ growth of NiFeM-LDH (M = Mo, mn, co, W, P, B, etc.) materials on a porous nickel substrate is realized by additionally arranging a vacuum adsorption heating platform on a screen printer. The advantages of the characteristics are as follows: (1) In-situ growth is carried out in the instantaneous process of screen printing to form a three-dimensional NiFeM-LDH self-supporting structure without noble metal load. (2) The prepared NiFeM-LDH electrode has higher OER activity and stability in an alkaline medium. (3) The screen printing process is simple, the quality control is easy to realize, the process repeatability is good, and the prepared oxygen evolution anode has higher repeatability and uniformity and is suitable for batch preparation of large-area OER electrodes.
The invention provides the following technical scheme, which comprises the following specific steps:
a silk-screen printing preparation method of a self-supporting oxygen evolution anode comprises the following steps:
(1) Substrate pretreatment: taking a porous nickel-based material as an electrode substrate, respectively cleaning the electrode substrate in acetone, absolute ethyl alcohol and deionized water, then etching the electrode substrate in water-soluble acid, and finally drying the electrode substrate at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: dissolving nickel salt and iron salt in deionized water to prepare a metal salt solution or dissolving nickel salt, iron salt and a third component M salt in deionized water to prepare a metal salt solution; dissolving a water-soluble reducing agent in deionized water to prepare a reducing agent solution; the third component M is one or the mixture of more than two of Mo, mn, co, W, P and B.
(3) A temperature-controllable vacuum adsorption heating platform is additionally arranged on the printing plane of the silk screen printing machine; placing the porous nickel-based material on a heating table for fixing, and brushing a layer of the metal salt solution prepared in the step (2) on the porous nickel-based material by adopting a silk screen with the mesh number of 50-400 through a silk screen printing technology; then, adopting the reducing agent solution prepared in the step (2) as silk-screen slurry, and repeatedly and alternately silk-screening the metal salt solution and the reducing agent solution; and after silk-screen printing is finished, naturally drying at room temperature to obtain the self-supporting oxygen evolution anode of the NiFe alloy or the NiFeM alloy.
(4) And (3) heat treatment: and (4) placing the self-supporting oxygen evolution anode obtained in the step (3) in an oven protected by inert gas atmosphere, and performing heat treatment to obtain the self-supporting oxygen evolution anode of NiFe-LDH or NiFeM-LDH.
Further, in the step (1), the porous nickel-based material may be foamed nickel or nickel felt; the water-soluble acid can be one or more of diluted hydrochloric acid, oxalic acid and phosphoric acid.
Further, in the step (1), the concentration of the water-soluble acid used for etching is 5-20 wt.%, and the etching temperature is 80-100 ℃.
Further, in the step (2), the mass concentration of the nickel salt in the metal salt solution is 10 to 50 g.L -1 (ii) a The mass concentration of the ferric salt is 1-50 g.L -1 (ii) a The mass concentration of the third component M salt is 0-10 g.L -1 。
Further, in the step (2), the mass concentration of the reducing agent solution is 1 to 30 g.L -1 。
Further, in the step (2), the water-soluble reducing agent is one or a mixture of two or more of borohydride, hydrazine hydrate, ascorbic acid and glycol.
Further, in the step (3), the metal salt solution and the reducing agent solution are used for printing, and the volume ratio of the metal salt solution to the reducing agent solution is 1:1, the total coating amount per unit electrode area is 0.1-1 mL cm -2 。
Further, in the step (3), the heating temperature of the heating table is between 25 ℃ and 350 ℃.
Further, in the step (4), the heat treatment temperature is 200-500 ℃, and the annealing time is 2-10 h.
The invention has the following beneficial effects: (1) The method adopts a screen printing preparation process, has the advantages of simple process, easy realization of quality control, good process repeatability and the like, and is suitable for batch preparation of large-area OER electrodes; the prepared oxygen evolution anode has higher repeatability and uniformity and is far superior to commercial IrO 2 、RuO 2 The performance of the electrode can meet the requirements of industrial production. (2) The three-dimensional NiFeM-LDH self-supporting structure is formed by in-situ growth in the screen printing process, so that the problems of small specific surface area, poor electron transfer performance, low active site exposure and slow reaction kinetic process of the porous nickel-based material are effectively solved, the stability and the conductivity of the electrode are enhanced, and the release of an oxygen product is facilitated; the polymer adhesive which is not beneficial to conductivity is not needed, so that the conductivity is further enhanced; no noble metal load. (3) The method greatly improves the oxygen evolution catalysis performance through an etching process, a third component doping and a heat treatment process, and the obtained oxygen evolution anode has extremely high oxygen evolution activity, stability and repeatability: at 1 mol. L -1 When the current density is 10 mA-cm, the KOH electrolyte solution is used as an oxygen evolution anode material -2 When the current density is 1A cm, the oxygen evolution overpotential is 137mV -2 When the oxygen evolution overpotential is 277mV; in a stability test for 500 hours, at 500mA cm -2 Electricity (D) fromUnder the flow density, the performance decay rate is only 0.99mV/h; the relative error of activity of samples at different positions on the large-area electrode is below 5%.
Drawings
FIG. 1 is a schematic diagram of a screen printing process for preparing a self-supporting oxygen evolving anode according to the present invention.
FIG. 2 is a SEM image of an electrode prepared in example 1 of the present invention.
FIG. 3 is a plot of the polarization of an electrochemical oxygen evolving anode according to the effect of the third component M on the OER activity of the oxygen evolving anode in example 2 of the present invention.
FIG. 4 is a graph of electrochemical oxygen evolution anodic polarization with the effect of the acid concentration used for etching, the etching temperature, on the OER activity of the oxygen evolution anode in example 3 of the present invention.
FIG. 5 is a plot of electrochemical oxygen evolution anode polarization as a function of nickel salt concentration on the OER activity of the oxygen evolution anode in example 4 of the present invention.
FIG. 6 is a plot of electrochemical oxygen evolution anode polarization as a function of iron salt concentration on oxygen evolution anode OER activity in example 5 of the present invention.
FIG. 7 is a graph of the polarization curve of an electrochemical oxygen evolving anode showing the effect of the concentration of the metal salt of the third component M on the OER activity of the oxygen evolving anode in example 6 of the present invention.
FIG. 8 is a plot of electrochemical oxygen evolution anode polarization as a function of reducing agent concentration on oxygen evolution anode OER activity in example 7 of the present invention.
FIG. 9 is a plot of electrochemical oxygen evolution anode polarization as a function of the per electrode area application to the OER activity of the oxygen evolution anode in example 8 of the present invention.
FIG. 10 is an electrochemical oxygen evolving anode polarization curve showing the effect of heating temperature on the OER activity of the oxygen evolving anode in example 9 of the present invention.
FIG. 11 is a plot of electrochemical oxygen evolution anode polarization as a function of heat treatment temperature on oxygen evolution anode OER activity in example 10 of the present invention.
FIG. 12 is a graph of electrochemical oxygen evolution anodic polarization stability for electrodes prepared in example 11 of the present invention.
FIG. 13 is an electrochemical oxygen evolution anodic polarization curve for the electrode uniformity test prepared in example 12 of the present invention.
Detailed Description
The following further describes the specific embodiments of the present invention with reference to the drawings and technical solutions.
Example 1: SEM scanning electron microscope test of oxygen evolution anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the substrate into strip electrodes with the thickness of 6cm multiplied by 2cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing the electrodes with absolute ethyl alcohol and deionized water for 3 times, then etching the electrodes in 10wt.% of dilute hydrochloric acid at 100 ℃ for 10min, and finally drying the electrodes at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting manner: the substrate material was fixed on a heating table set at 80 ℃ with a mesh number of 400. After the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate by a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 250 ℃, and the annealing time is 2 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) The scanning electron microscope result is shown in fig. 2, and the prepared oxygen evolution electrode is in a lamellar self-supporting hydrotalcite structure.
Example 2: influence of the third component M on the OER Activity of the oxygen evolving Anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the foamed nickel into strips with the thickness of 6cm multiplied by 2cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing with absolute ethyl alcohol and deionized water for 3 times, then etching in 20wt.% phosphoric acid at 100 ℃ for 10min, and finally drying at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The third component respectively selects Mo, mn and Co to prepare NiFeMo-LDH, niFeMn-LDH and NiFeCo-LDH oxygen evolution anodes with the mass concentration of metal salt of 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting manner: the substrate material was fixed on a heated table set at 100 ℃ with a mesh of 50. And after the temperature is stable, coating a layer of metal salt solution on the porous nickel substrate by a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 300 ℃, and the annealing time is 2 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The results of the linear scan at a scan rate of 1mV/s are shown in FIG. 3. It is known that the addition of the third component M can increase the OER activity of the oxygen evolving anode.
Example 3: influence of etching acid concentration and etching temperature on OER activity of oxygen evolution anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the foamed nickel into strips of 6cm multiplied by 2cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing the strips with absolute ethyl alcohol and deionized water for 3 times, then respectively etching the strips in 5wt.% oxalic acid at 80 ℃ for 10min, 10wt.% oxalic acid at 90 ℃ for 10min, and etching the strips in 20wt.% oxalic acid at 100 ℃ for 10min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting way: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 100 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 300 ℃, and the annealing time is 5h. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the test temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The linear scan was performed at a scan rate of 1mV/s, and the results are shown in FIG. 4. It is known that the OER activity of the oxygen evolution anode can be improved by increasing the concentration of the acid used for etching and the etching temperature.
Example 4: influence of nickel salt concentration on OER activity of oxygen evolution anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking a nickel felt with the thickness of 0.3mm as a substrate, cutting the nickel felt into strips with the thickness of 6cm multiplied by 2cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing the strips with absolute ethyl alcohol and deionized water for 3 times, then etching the strips in 10wt.% of dilute hydrochloric acid at 100 ℃ for 10min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 10 g.L -1 、30g·L -1 、50g·L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting way: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 100 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 300 ℃, and the annealing time is 5 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (4) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The linear scan was performed at a scan rate of 1mV/s, and the test results are shown in FIG. 5, which indicates that the increase in the concentration of nickel salt can increase the OER activity of the oxygen evolution anode.
Example 5: effect of iron salt concentration on OER Activity of oxygen evolving Anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm-1.5mm as a substrate, cutting the foamed nickel into strips of 6cm multiplied by 2cm, ultrasonically treating the strips in acetone for 30min, sequentially washing the strips with absolute ethyl alcohol and deionized water for 3 times, then etching the strips in 10wt.% of dilute hydrochloric acid at 100 ℃ for 10min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing a metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 1 g.L -1 、25g·L -1 、50g·L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting manner: and (3) placing the substrate material on a heating table for fixing, setting the temperature of the heating table to be 80 ℃, and after the temperature is stable, brushing a layer of metal salt solution on the porous nickel substrate by a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. And after finishing coating, naturally drying the electrode at room temperature to obtain the target oxygen evolution catalyst electrode.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 300 ℃, and the annealing time is 5 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The results of the linear scan at a scan rate of 1mV/s are shown in FIG. 6. It is known that the OER activity of the oxygen evolution anode is firstly increased and then decreased along with the increase of the concentration of the ferric salt, and the mass concentration of the ferric salt is 25 g.L -1 The OER activity was highest.
Example 6: effect of third component M Metal salt concentration on oxygen evolution Anode OER Activity
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking a nickel felt with the thickness of 0.4mm as a substrate, cutting the nickel felt into strips of 6cm multiplied by 2cm, ultrasonically treating the strips in acetone for 30min, then sequentially washing the strips for 3 times by using absolute ethyl alcohol and deionized water, then etching the strips in 20wt.% phosphoric acid at 100 ℃ for 10min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing a metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 0, 5 g.L -1 、10g·L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting way: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 100 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 250 ℃, and the annealing time is 5 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The linear scan was performed at a scan rate of 1mV/s, and the results are shown in FIG. 7. It is known that the increase of the concentration of the metal salt of the third component M can improve the OER activity of the oxygen evolution anode.
Example 7: effect of reducing agent concentration on OER Activity of oxygen evolving anodes
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the foamed nickel into strips with the thickness of 6cm multiplied by 2cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing the strips with absolute ethyl alcohol and deionized water for 3 times, then etching the strips in 20wt.% oxalic acid at 100 ℃ for 10min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 1 g.L -1 、10g·L -1 、30g·L -1 。
(3) Preparing an electrode in a self-supporting manner: and (3) placing the substrate material on a heating table for fixing, setting the temperature of the heating table to be 80 ℃, and after the temperature is stable, brushing a layer of metal salt solution on the porous nickel substrate by a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. And after the painting is finished, naturally drying the electrode at room temperature to obtain the target oxygen evolution catalyst electrode.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 250 ℃, and the annealing time is 10 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (4) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The results of the linear scan at a scan rate of 1mV/s are shown in FIG. 8. It is known that an increase in the concentration of the reducing agent can increase the OER activity of the oxygen evolving anode.
Example 8: influence of unit electrode area coating quantity on OER activity of oxygen evolution anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the foamed nickel into strips of 6cm multiplied by 2cm, ultrasonically treating the strips in acetone for 30min, then sequentially washing the strips for 3 times by using absolute ethyl alcohol and deionized water, then etching the strips in 10wt.% of dilute hydrochloric acid at 100 ℃ for 60min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparation of Metal salt solutionWherein the mass concentration of the nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing ascorbic acid solution with mass concentration of 5 g.L -1 。
(3) Preparing an electrode in a self-supporting way: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 80 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. And after finishing coating, naturally drying the electrode at room temperature to obtain the target oxygen evolution catalyst electrode. The amount of the solution used was controlled so that the amount of coating per unit area of the electrode was 0.1mL cm -2 、0.5mL·cm -2 、1mL·cm -2 。
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 250 ℃, and the annealing time is 10 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The results of the linear scan at a scan rate of 1mV/s are shown in FIG. 9. It is known that the increase of the coating amount per click area can improve the OER activity of the oxygen evolution anode.
Example 9: effect of heating temperature on OER Activity of oxygen evolving Anode
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the foamed nickel into strips of 6cm multiplied by 2cm, ultrasonically treating the strips in acetone for 30min, then sequentially washing the strips with absolute ethyl alcohol and deionized water for 3 times, then etching the strips in 10wt.% phosphoric acid at 100 ℃ for 60min, and finally drying the strips at room temperature for later use.
(2) Preparation of metal salt solution and reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing hydrazine hydrate solution with the mass concentration of 1 g.L -1 。
(3) Preparing an electrode in a self-supporting way: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 25 ℃,100 ℃ and 350 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 350 ℃, and the annealing time is 2 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the test temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The linear scan was performed at a scan rate of 1mV/s, and the results are shown in FIG. 10. It is known that an increase in the heating temperature can increase the OER activity of the oxygen evolving anode.
Example 10: influence of Heat treatment temperature on OER Activity of oxygen evolving anodes
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking foamed nickel with the thickness of 0.3mm as a substrate, cutting the foamed nickel into strips of 6cm multiplied by 2cm, ultrasonically treating the strips in acetone for 30min, then sequentially washing the strips for 3 times by using absolute ethyl alcohol and deionized water, then etching the strips in 10wt.% of dilute hydrochloric acid at 100 ℃ for 10min, and finally drying the strips at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 Of salts of metals of the third componentThe mass concentration is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting manner: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 100 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 200 ℃, 350 ℃,500 ℃, and the annealing time is 2h. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) performance testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . The results of the linear scan at a scan rate of 1mV/s are shown in FIG. 11. It is known that the increase of the heat treatment temperature can improve the OER activity of the oxygen evolution anode.
Example 11: oxygen evolution anode OER stability test
(1) Substrate pretreatment: taking a nickel felt with the thickness of 0.3mm as a substrate, cutting the nickel felt into sheets with the thickness of 6cm multiplied by 8cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing the sheets with absolute ethyl alcohol and deionized water for 3 times, then etching the sheets in 10wt.% phosphoric acid at 100 ℃ for 10min, and finally drying the sheets at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing glycol solution with mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting manner: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 100 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 500 ℃, and the annealing time is 2 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (3) stability testing: placing a target oxygen evolution electrode in an H-shaped electrolytic cell, wherein the electrolyte is 1MKOH, a reference electrode is a saturated calomel electrode, and a counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20mL·min -1 . At 500mA.cm -2 The stability of the electrode was tested under constant current conditions for 500h, and the test results are shown in fig. 12. Therefore, the oxygen evolution anode prepared by silk-screen printing has better stability, and the stability in a 500-hour stability test is 500 mA-cm -2 The performance decay rate is only 0.99mV/h at the current density of (1).
Example 12: oxygen evolution anode OER uniformity test
The self-supporting oxygen evolution anode is prepared by the following preparation process:
(1) Substrate pretreatment: taking a nickel felt with the thickness of 0.3mm as a substrate, cutting the nickel felt into sheets with the thickness of 6cm multiplied by 8cm, carrying out ultrasonic treatment in acetone for 30min, then sequentially washing the sheets with absolute ethyl alcohol and deionized water for 3 times, then etching the sheets in 20wt.% oxalic acid at 100 ℃ for 10min, and finally drying the sheets at room temperature for later use.
(2) Preparing a metal salt solution and a reducing agent solution: preparing metal salt solution, wherein the mass concentration of nickel salt is 30 g.L -1 The mass concentration of the iron salt is 30 g.L -1 The mass concentration of the third component metal salt is 5 g.L -1 (ii) a Preparing sodium borohydride solution with the mass concentration of 20 g.L -1 。
(3) Preparing an electrode in a self-supporting manner: the substrate material is placed on a heating table and fixed, the temperature of the heating table is set to be 100 ℃, and after the temperature is stable, a layer of metal salt solution is coated on the porous nickel substrate through a screen printing technology. Then, a water-soluble reducing agent solution is adopted for fast coating, and after the surface of the substrate is dried, the metal salt solution and the reducing agent solution are repeatedly and alternately coated. After painting, the paint is naturally dried at room temperature.
(4) Heat treatment after preparation: and transferring the substrate with the catalyst to a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment starting temperature is 25 ℃, the heat treatment temperature is 350 ℃, and the annealing time is 2 hours. And obtaining the target oxygen evolution electrode after the heat treatment is finished.
(5) And (4) performance testing: uniformly cutting the target oxygen evolution electrode into 8 strips of 1cm multiplied by 6cm, respectively placing the strips in an H-shaped electrolytic cell, wherein the electrolyte is selected from 1MKOH, the reference electrode is a saturated calomel electrode, and the counter electrode is a platinum electrode; the testing temperature is 25 ℃, O is introduced into the anode 2 20 mL·min -1 . The linear scan was performed at a scan rate of 1mV/s, and the results are shown in FIG. 13. Therefore, the large-area oxygen evolution anode prepared by silk screen printing has better uniformity, and the relative error of the activity of samples at different positions is less than 5%.
Claims (9)
1. A silk-screen printing preparation method of a self-supporting oxygen evolution anode is characterized by comprising the following steps:
(1) Substrate pretreatment: taking a porous nickel-based material as an electrode substrate, respectively cleaning the electrode substrate in acetone, absolute ethyl alcohol and deionized water, then etching the electrode substrate in water-soluble acid, and finally drying the electrode substrate at room temperature for later use;
(2) Preparing a metal salt solution and a reducing agent solution: dissolving nickel salt and iron salt in deionized water to prepare a metal salt solution or dissolving nickel salt, iron salt and a third component M salt in deionized water to prepare a metal salt solution; dissolving a water-soluble reducing agent in deionized water to prepare a reducing agent solution; the third component M is one or a mixture of more than two of Mo, mn, co, W, P and B;
(3) A temperature-controllable vacuum adsorption heating platform is additionally arranged on a printing plane of the screen printing machine; fixing the porous nickel-based material on a heating table, and brushing a layer of the metal salt solution prepared in the step (2) on the porous nickel-based material by adopting a silk screen with the mesh number of 50-400 through a silk screen printing technology; then, adopting the reducing agent solution prepared in the step (2) as silk-screen slurry, and repeatedly and alternately silk-screening the metal salt solution and the reducing agent solution; after finishing silk-screen printing, naturally drying at room temperature to obtain a self-supporting oxygen evolution anode of NiFe alloy or NiFeM alloy;
(4) And (3) heat treatment: and (4) placing the self-supporting oxygen evolution anode obtained in the step (3) in an oven protected by inert gas atmosphere, and performing heat treatment to obtain the self-supporting oxygen evolution anode of NiFe-LDH or NiFeM-LDH.
2. The method for preparing a self-supporting oxygen evolution anode by screen printing according to claim 1, wherein in the step (1), the porous nickel-based material is foamed nickel or nickel felt; the water-soluble acid is one or more of diluted hydrochloric acid, oxalic acid and phosphoric acid.
3. The method for preparing a self-supporting oxygen evolution anode by screen printing according to claim 1 or 2, wherein in the step (1), the concentration of the water-soluble acid used for etching is between 5 and 20wt.%, and the etching temperature is between 80 and 100 ℃.
4. The process for preparing self-supporting oxygen evolution anode by screen printing as claimed in claim 1 or 2, wherein in the step (2), the mass concentration of the nickel salt in the metal salt solution is 10-50 g-L -1 (ii) a The mass concentration of the ferric salt is 1-50 g.L -1 (ii) a The mass concentration of the third component M salt is 0-10 g.L -1 。
5. The process according to claim 1 or 2, characterized in that in step (2), the mass concentration of the reducing agent solution is 1-30 g.L -1 。
6. The method according to claim 1 or 2, wherein in the step (2), the water-soluble reducing agent is one or a mixture of two or more of borohydride, hydrazine hydrate, ascorbic acid and ethylene glycol.
7. The process for preparing self-supporting oxygen evolving anode by screen printing according to claim 1 or 2, wherein in the step (3), the metal salt solution and the reducing agent solution are used for printing in a volume ratio of 1:1, the total coating amount per unit electrode area is 0.1-1 mL cm -2 。
8. The process for the screen-printing preparation of a self-supporting oxygen evolving anode according to claim 1 or 2 characterized in that in step (3) the heating stage is heated to a temperature between 25 ℃ and 350 ℃.
9. The screen printing preparation method of the self-supporting oxygen evolution anode according to the claim 1 or 2, characterized in that, in the step (4), the heat treatment temperature is between 200 ℃ and 500 ℃ and the annealing time is 2-10 h.
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